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The electro-optical Kerr effect of n-alkanes from C(5) to C(16) was investigated in gas phase, liquid phase, and solution. The values of the Kerr constants in gas phase are noticeably distinguishable from those in liquids, where the molecules interact by the London dispersion forces. Both the energy of the dispersion interaction and the difference in the Kerr constants in liquid and gas phase grow with molecular size, indicating the key influence of the interaction on the magnitude of the Kerr effect. Several orientation and molecular-statistical theories of electro-optical Kerr effect were applied to model the change in electro-optical Kerr effect due to the dispersion force. Most theories show significant divergence compared to the experimental data. It is argued that the decisive contribution to electro-optical Kerr effect in liquids and the deviations between the experiment and theory arise due to local liquid structures that collectively orient in the external electric field.

The Role of Intermolecular Interactions in the Electro-Optical Kerr Effect in Liquid Alkanes